Murff entered the majors in 1956 with the Braves as a 35-year-old rookie, having been signed by Milwaukee scout Earle W. Halstead. In a story chronicled in Murff's biography "The Scout", Halstead negotiated with Dick Burnett, owner of the Dallas Eagles in the Texas League, where Murff played. The two sides reached an impasse until Halstead proposed a game of gin rummy with the winner setting the terms of the trade. Halstead won and the Braves paid Burnett $40,000 and three players from the 40 man roster to obtain Murff's contract. In part of two seasons, he posted a 2–2 record with a 4.65 ERA and three saves in 26 appearances, including two starts, giving up 26 earned runs on 56 hits and 18 walks while striking out 31 in 50+1⁄3 innings of work.
In the early 1970s, Murff helped start the University of Mary Hardin-Baylor baseball program, and retired to Tyler, Texas, in 1991 after serving 34 years as a scout. He was inducted into the Texas Baseball Hall of Fame in 1989 and the Texas Scouts Association Hall of Fame in 1999, and in 1994 the UMHB's ballpark was named in his honour, Red Murff Field.
Murff died in a Tyler nursing home at the age of 87.